Substituted heterocyclic methine dyes

ABSTRACT

Disclosed are disperse dyes for the dyeing of synthetic fibers such as cellulose acetate, triacetate, polyamide and especially polyester and its blends, which have the general formula ##STR1## in which R 1  and R 2  may be the same or different and are selected, for example, from hydrogen, aryl, benzyl, cyclohexyl, and C 1  -C 6  alkyl optionally substituted by Cl, CN, OC 2  H 4  OC 2  H 5 , C 1  -C 4  alkoxy, aryl, ##STR2## NHCONHPh, OCONHPh, phthalimido, succinimido or mercaptobenzthiazolyl, and R 1  and R 2  may form a 5- or 6-membered ring with the ##STR3## which ring may or may not contain a S, N, or O atom; R 3  is H, Cl, Br, C 1  -C 4  alkyl or C 1  -C 4  alkoxy; R 2  and R 3  may form a 5 or 6 membered ring preferably substituted by 1-3 methyl groups; R 4  is H, Cl, Br, C 1  -C 4  alkyl or C 1  -C 4  alkoxy; and R 5  is selected from 3-pyridyl, 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl and 2-thienyl, which R 5  heterocycles may be substituted by Cl, Br, NO 2 , CN, aryl, aryl substituted by Cl, Br, NO 2  or CN, C 1  -C 4  alkyl or COOR 6  wherein R 6  is C 1  -C 4  alkyl or aryl.

This invention relates to disperse dyes for the dyeing of synthetic fibers such as cellulose acetate, triacetate, polyamide and especially polyester and its blends, which have the general formula ##STR4## in which R₁ and R₂ may be the same or different and are selected from hydrogen, aryl, benzyl, cyclohexyl, and C₁ -C₆ alkyl which may be substituted by Cl, CN, OC₂ H₄ OC₂ H₅, C₁ -C₄ alkoxy, aryl, ##STR5## (in which the aryl, and the C₁ -C₁₀ alkyl of the preceding substituent, may be substituted by Cl, Br, CN, NO₂, CO--alkyl, CO--aryl, alkoxy, aryloxy, CO--O--alkyl or CO--O--aryl), ##STR6## NHCONHPh, OCONHPh, phthalimido, succinimido or mercaptobenzthiazolyl, and R₁ and R₂ may form a 5- or 6-membered ring with the ##STR7## which ring may or may not contain a S, N, or O atom; R₃ is H, Cl, Br, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; R₂ and R₃ may form a 5 or 6 membered ring preferably substituted by 1-3 methyl groups; R₄ is H, Cl, Br, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; and R₅ is selected from 3-pyridyl, 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl and 2-thienyl, which R₅ heterocycles may be substituted by Cl, Br, NO₂, CN, aryl, aryl substituted by Cl, Br, NO₂ or CN, C₁ -C₄ alkyl or COOR₆ wherein R₆ is C₁ -C₄ alkyl or aryl.

The dyes produce yellow to scarlet shades on hydrophobic textile fiber including polyesters, polyamides and cellulose esters and show unexpected improvements in one or more of such properties as fastness to light, wash, ozone, gas such as oxides of nitrogen, perspiration, crock, sublimation, dyeability at unusually low energy levels to deep shades and exhibit excellent build, pH stability, bloom resistance, leveling, migration, dye bath exhaustion, dye transfer, heat stability on polyamide and the like, over such prior art as disclosed in U.S. Pat. Nos. 4,077,962; 4,016,191; 4,006,178; 3,917,604; 3,240,783; 3,247,211; 3,595,863; 3,453,280; 2,766,233; 2,850,520; and Japanese J7-4023-806.

The dyeing of the fiber with the dyestuffs according to the invention is appropriately carried out from an aqueous suspension in the presence of carriers between 80° and 100° C., in the absence of carriers at between 100°-130° C., or using the so-called thermofixing process at 180°-230° C. The printing of the materials can be carried out by steaming the goods, printed with the new dyestuffs, in the presence of a carrier at temperatures between 80° and 110° C., or in the absence of a carrier at 110°-140° C., or also by treating the goods which have been printed with the new dyestuffs, according to the thermofixing process at 180°-230° C.

This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

EXAMPLE 1

4-Formyl N-ethyl-N-(β-cyanoethyl) aniline (0.404 g, 0.002 mole) was dissolved in ethyl alcohol (10 ml). To this was added 5-chloro-benzoxazolyl-2-acetonitrile (0.385 g, 0.002 mole) and piperidine (0.1 ml) and the mixture was warmed on a steam bath for 15 min. After cooling overnight the orange crystalline product was collected by filtration and air dried. The dye was ball milled in the presence of a lignin sulphonate dispersing agent for 24 hours and the resulting dispersion was applied to polyester fiber by dyeing at 130° for 1 hour. It gave a deep yellow dyeing of excellent color strength and fastness to light. Similar dyeings prepared in dyebaths buffered from pH 4-8 also gave high strength dyeings indicating the dye had excellent pH stability.

EXAMPLE 2

4-Formyl N-ethyl N-(2'-phthalimidoethyl) m-toluidine (1.68 g., 0.005 g. mole) was dissolved in ethyl alcohol (40 ml). To this was added 2-quinoxalyl acetonitrile (0.85 g., 0.005 g. mole) with stirring, and piperidine (0.2 ml) was added and the mixture left at room temperature overnight. The orange crystalline product was collected by filtration, washed with a little cold ethanol and dried. The dye was ball milled in the presence of a lignin sulphonate dispersing agent for 24 hours and the resulting dispersion was applied to polyester fibre by dyeing at 130° for 1 hour. It gave a deep yellow dyeing of excellent color strength and fastness to light. Similar dyeings prepared in dyebaths buffered from pH 4-8 also gave high strength dyeings indicating the dye had excellent pH stability.

By application of the synthetic procedures outlined in Example 1, the following dyes were prepared. When applied by a procedure similar to the above dyeing description they give high strength dyeings on polyester textile fibers.

    __________________________________________________________________________     Methine Dyestuffs of the Formula                                                ##STR8##                                                                      Example                                                                             R.sub.1     R.sub.2   R.sub.3                                                                            R.sub.4                                                                            R.sub.5                                     __________________________________________________________________________     3    C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro-                                                                      benzoxazolyl                                      ##STR9##   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      5                                                                                    ##STR10##  C.sub.2 H.sub.5                                                                          Br  CH.sub.3                                                                           5-chloro- benzoxazolyl                      6    C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-cyano-                                                                       benzoxazolyl                                7                                                                                    ##STR11##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-cyano- benzoxazolyl                       8    Ph          CH.sub.2 Ph                                                                              H   H   5-bromo-                                                                       benzoxazolyl                                9    C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   H   5-nitro-                                                                       benzoxazolyl                                10   C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro-                                                                       benzoxazolyl                                11   C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                          CH.sub.3                                                                           OCH.sub.3                                                                          5-nitro-                                                                       benzoxazolyl                                12   C.sub.2 H.sub.4 Cl                                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         CH.sub.3                                                                           OCH.sub.3                                                                          5-nitro-                                                                       benzoxazolyl                                13   CH.sub.2 Ph C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         Cl  Cl  5-nitro-                                                                       benzoxazolyl                                14                                                                                   ##STR12##  C.sub.3 H.sub.7                                                                          H   H   5-cyano- benzoxazolyl                       15                                                                                   ##STR13##  C.sub.3 H.sub.7                                                                          H   Br  5-cyano- benzoxazolyl                       16   CH.sub.2 C.sub.6 H.sub.5                                                                   C.sub.2 H.sub.4 Cl                                                                       H   H   5-methyl-                                                                      benzoxazolyl                                17   CH.sub.2 C.sub.6 H.sub.5                                                                   CH.sub.2 C.sub.6 H.sub.5                                                                 CH.sub.3                                                                           CH.sub.3                                                                           5-COOCH.sub.3 --                                                               benzoxazolyl                                18   C.sub.2 H.sub.4 OCONHPh                                                                    CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           5-COOCH.sub.3 --                                                               benzoxazolyl                                19                                                                                   ##STR14##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro- benzoxazolyl                       20   C.sub.6 H.sub.11                                                                           C.sub.2 H.sub.4 CN                                                                       H   CH.sub.3                                                                           5-nitro-                                                                       benzoxazolyl                                21   C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro-                                                                       benzoxazolyl                                22   C.sub.2 H.sub.4 Ph                                                                         C.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   5-nitro-                                                                       benzoxazolyl                                23   H           C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro-                                                                      benzothiazolyl                              24                                                                                   ##STR15##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzothiazolyl                    25                                                                                   ##STR16##            H   CH.sub.3                                                                           5-chloro- benzothiazolyl                    26   C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro-                                                                      benzothiazolyl                              27                                                                                   ##STR17##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzothiazolyl                    28   Ph          Ph        H   H   5-chloro-                                                                      benzothiazolyl                              29   C.sub.2 H.sub.4 CN                                                                         H         H   H   5-nitro-                                                                       benzothiazolyl                              30   C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro-                                                                       benzothiazolyl                              31   H           C.sub.2 H.sub.5                                                                          CH.sub.3                                                                           OCH.sub.3                                                                          5-nitro-                                                                       benzothiazolyl                              32   C.sub.2 H.sub.4 Cl                                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                        CH.sub.3                                                                           OCH.sub.3                                                                          5-nitro-                                                                       benzothiazolyl                              33   "           C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         Cl  Cl  5-nitro-                                                                       benzothiazolyl                              34                                                                                   ##STR18##            H   H   5-cyano- benzothiazolyl                     35                                                                                   ##STR19##            H   H   5-cyano- benzothiazolyl                     36   C.sub.6 H.sub.11                                                                           C.sub.2 H.sub.4 CN                                                                       H   H   5-methyl-                                                                      benzothiazolyl                              37   CH.sub.2C.sub.6 H.sub.5                                                                    C.sub.2 H.sub.5                                                                          CH.sub.3                                                                           CH.sub.3                                                                           5-COOCH.sub.3 --                                                               benzothiazolyl                              38   C.sub.2 H.sub.4 OCONHPh                                                                    CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           5-COOC.sub.6 H.sub.5 --                                                        benzothiazolyl                              39                                                                                   ##STR20##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro- benzothiazolyl                     40   C.sub.6 H.sub.11                                                                           C.sub.6 H.sub.11                                                                         H   CH.sub.3                                                                           5-nitro-                                                                       benzothiazolyl                              41   C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-nitro-                                                                       benzothiazolyl                              42   C.sub.2 H.sub.4 Ph                                                                         C.sub.2 H.sub.5                                                                          OC.sub. 2 H.sub.5                                                                  OC.sub.2 H.sub.5                                                                   5-nitro-                                                                       benzothiazolyl                              43   C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 44                                                                                   ##STR21##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 45                                                                                   ##STR22##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 46   C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 47                                                                                   ##STR23##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 48   Ph          Ph        H   H   5-phenyl-1,3,4-                                                                oxadiazolyl                                 49   C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   H   5-phenyl-1,3,4-                                                                oxadiazolyl                                 50   C.sub.2 H.sub.4 CN                                                                         C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 51   C.sub.2 H.sub.4 Cl                                                                         C.sub.2 H.sub.5                                                                          CH.sub.3                                                                           OCH.sub.3                                                                          5-phenyl-1,3,4-                                                                oxadiazolyl                                 52   C.sub.2 H.sub.4 Cl                                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         CH.sub.3                                                                           OCH.sub.3                                                                          5-phenyl-1,3,4-                                                                oxadiazolyl                                 53                                                                                   ##STR24##  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         Cl  Cl  5-phenyl-1,3,4- oxadiazolyl                 54                                                                                   ##STR25##  C.sub.3 H.sub.7                                                                          H   H   5-phenyl-1,3,4- oxadiazolyl                 55                                                                                   ##STR26##            H   H   5-phenyl-1,3,4- oxadiazolyl                 56                                                                                   ##STR27##            H   H   5-phenyl-1,3,4- oxadiazolyl                 57                                                                                   ##STR28##            CH.sub.3                                                                           CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 58   C.sub.2 H.sub.4 OCONHPh                                                                    CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 59                                                                                   ##STR29##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 60   CH.sub.2 C.sub.6 H.sub.5                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 61   C.sub.2 H.sub.4 NHCONHPh                                                                   C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-phenyl-1,3,4-                                                                oxadiazolyl                                 62   C.sub.2 H.sub.4 Ph                                                                         C.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   5-phenyl-1,3,4-                                                                oxadiazolyl                                 63                                                                                   ##STR30##  C.sub.2 H.sub.5                                                                          H   H   5-chloro- benzoxazolyl                      64   "           C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro-                                                                      benzoxazolyl                                65   "           CH.sub.2 Ph                                                                              H   CH.sub.3                                                                           5-chloro-                                                                      benzoxazolyl                                66   "           C.sub.4 H.sub.9                                                                          H   CH.sub.3                                                                           benzothiazolyl                              67                                                                                   ##STR31##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      68   "           C.sub.2 H.sub.5                                                                          H   H   benzothiazolyl                              69   "           C.sub.2 H.sub.4 CN                                                                       H   H   "                                           70   "                                                                                           ##STR32##                                                                               H   CH.sub.3                                                                           "                                           71                                                                                   ##STR33##  C.sub.2 H.sub.4 CN                                                                       H   H   5-chloro- benzoxazolyl                      72                                                                                   ##STR34##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      73                                                                                   ##STR35##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      74                                                                                   ##STR36##  C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      75                                                                                   ##STR37##  C.sub.2 H.sub.5                                                                          H   H   5-phenyl- 1,3,4-oxadiazolyl                 76   "           C.sub.2 H.sub.5                                                                          H   CH.sub.3                                                                           benzothiazolyl                              77   "           C.sub.2 H.sub.5                                                                          H   H   "                                           __________________________________________________________________________

    ______________________________________                                         Methine Dyestuffs of the Formula                                                ##STR38##                                                                     Example                                                                               R.sub.1           R.sub.4 R.sub.5                                       ______________________________________                                         78     C.sub.2 H.sub.4 OCONHPh                                                                          H       5-chloro-                                                                      benzoxazolyl                                  79     C.sub.2 H.sub.4 OCONHPh                                                                          CH.sub.3                                                                               5-chloro-                                                                      benzoxazolyl                                  80     C.sub.2 H.sub.4 Cl                                                                               H       5-chloro-                                                                      benzoxazolyl                                  81     C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                                 H       5-chloro-                                                                      benzoxazolyl                                  82     C.sub.2 H.sub.4 CN                                                                               H       5-chloro-                                                                      benzoxazolyl                                  83     C.sub.2 H.sub.4 CN                                                                               CH.sub.3                                                                               5-chloro-                                                                      benzoxazolyl                                  84                                                                                     ##STR39##        H       5-chloro- benzoxazolyl                        85                                                                                     ##STR40##        Br      5-chloro- benzoxazolyl                        86     C.sub.6 H.sub.5   H       5-chloro-                                                                      benzoxazolyl                                  87     C.sub.2 H.sub.4 OCONHPh                                                                          Cl      5-chloro-                                                                      benzothiazolyl                                88     C.sub.2 H.sub.4 NHCONHPh                                                                         CH.sub.3                                                                               5-chloro-                                                                      benzothiazolyl                                89     C.sub.2 H.sub.4 OCH.sub.3                                                                        H       5-chloro-                                                                      benzothiazolyl                                90     C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                OCH.sub.3                                                                              5-chloro-                                                                      benzothiazolyl                                91     C.sub.2 H.sub.4 CN                                                                               H       5-chloro-                                                                      benzothiazolyl                                92     H                 CH.sub.3                                                                               5-chloro-                                                                      benzothiazolyl                                93                                                                                     ##STR41##        H       5-chloro- benzothiazolyl                      94     CH.sub.2C.sub.6 H.sub.5                                                                          Cl      5-chloro-                                                                      benzothiazolyl                                95     C.sub.2 H.sub.5   H       5-chloro-                                                                      benzothiazolyl                                96     C.sub.2 H.sub.4 OCONHPh                                                                          H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   97     C.sub.2 H.sub.4 OCONHPh                                                                          CH.sub.3                                                                               5-phenyl-1,3,4-                                                                oxadiazolyl                                   98     C.sub.2 H.sub.4 Cl                                                                               H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   99     C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   100    C.sub.2 H.sub.4 CN                                                                               H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   101    C.sub.2 H.sub.4 CN                                                                               CH.sub.3                                                                               5-phenyl-1,3,4-                                                                oxadiazolyl                                   102                                                                                    ##STR42##        H       5-phenyl-1,3,4- oxadiazolyl                   103                                                                                    ##STR43##        H       5-phenyl-1,3,4- oxadiazolyl                   104    C.sub.2 H.sub.5   H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   ______________________________________                                    

The following table gives further examples and specifies the heterocyclic aldehyde which is reacted with the methylene active cyano compound.

    __________________________________________________________________________          Heterocyclic                                                              Example                                                                             acetonitrile                                                                             Aldehyde                                                        __________________________________________________________________________     105  3-Benzoisothiazolyl                                                                      6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          106  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     107  "         4-Formyl-N,N-diethylaniline                                     108  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         109  "         4-Formyl-N,N-diethyl-m-toluidine                                110  "         4-Formyl-N,N-diethyl-m-chloroaniline                            111  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     112  "         4-Formyl-N,N-diethyl-o-bromoaniline                             113  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    114  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         115  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)aniline                              116  "         4-Formyl-N,N-dibenzyl aniline                                   117  "         4-Formyl-N-phenylthiomorpholinedioxide                          118  3-pyridyl 6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          119  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     120  "         4-Formyl-N,N-diethylaniline                                     121  "         4-Formyl-N-ethyl                                                               N-(β-phthalaimidoethyl)-m-toluidine                        122  "         4-Formyl-N,N-diethyl-m-toluidine                                123  "         4-Formyl-N,N-diethyl-m-chloroaniline                            124  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     125  "         4-Formyl-N,N-diethyl-o-bromoaniline                             126  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    127  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         128  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             129  "         4-Formyl-N,N-dibenzyl aniline                                   130  "         4-Formyl-N-(β-acetoxyethyl)-N-ethylaniline                 131  "         4-Formyl-N-phenylthiomorpholinedioxide                          132  2-benzothiazolyl                                                                         6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          133  "         6-Formyl-N-(β  -mercaptobenzthiazolylethyl)                               1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     134  "         4-Formyl-N,N-diethylaniline                                     135  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         136  "         4-Formyl-N,N-diethyl-m-toluidine                                137  "         4-Formyl-N,N-diethyl-m-chloroaniline                            138  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     139  "         4-Formyl-N,N-diethyl-o-bromoaniline                             140  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    141  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         142  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             143  "         4-Formyl-N,N-dibenzyl aniline                                   144  "         4-Formyl-N-(β-butyloxyethyl)-N-ethylaniline                145  "         4-Formyl-N-phenylthiomorpholinedioxide                          146  2-benzoxazolyl                                                                           6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          147  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     148  "         4-Formyl-N,N-diethylaniline                                     149  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         150  "         4-Formyl-N,N-diethyl-m-toluidine                                151  "         4-Formyl-N,N-diethyl-m-chloroaniline                            152  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     153  "         4-Formyl-N,N-diethyl-o-bromoaniline                             154  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    155  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         156  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             157  "         4-Formyl-N,N-dibenzyl-aniline                                   158  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-succin-                             imidoethyl)-m-toluidine                                         159  "         4-Formyl-N-phenylthiomorpholinedioxide                          160  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-m-                               toluidine                                                       161  2-quinoxalyl                                                                             6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          162  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     163  "         4-Formyl-N,N-diethylaniline                                     164  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         165  "         4-Formyl-N,N-diethyl-m-toluidine                                166  "         4-Formyl-N,N-diethyl-m-chloroaniline                            167  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     168  "         4-Formyl-N,N-diethyl-o-bromoaniline                             169  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    170  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         171  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             172  "         4-Formyl-N,N-dibenzyl aniline                                   173  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-                                    succinimidoethyl)-m-toluidine                                   174  "         4-Formyl-N-phenylthiomorpholinedioxide                          175  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-                                 m-toluidine                                                     176  2-quinazolinonyl                                                                         6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          177  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     178  "         4-Formyl-N,N-diethylaniline                                     179  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         180  "         4-Formyl-N,N-diethyl-m-toluidine                                181  "         4-Formyl-N,N-diethyl-m-chloroaniline                            182  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     183  "         4-Formyl-N,N-diethyl-o-bromoaniline                             184  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    185  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         186  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             187  "         4-Formyl-N,N-dibenzyl aniline                                   188  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-                                    succinimidoethyl)-m-toluidine                                   189  "         4-Formyl-N-phenylthiomorpholinedioxide                          190  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-                                 m-toluidine                                                     191  2-1,3,4-oxadiazolyl                                                                      6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          192  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     193  "         4-Formyl-N,N-diethylaniline                                     194  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         196  "         4-Formyl-N,N-diethyl-m-chloroaniline                            197  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     198  "         4-Formyl-N,N-diethyl-o-bromoaniline                             199  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    200  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         201  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             202  "         4-Formyl-N,N-dibenzyl aniline                                   203  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-                                    succinimidoethyl)-m-toluidine                                   204  "         4-Formyl-N-phenylthiomorpholinedioxide                          205  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-                                 m-toluidine                                                     206  2-1,3,4-thiadiazolyl                                                                     6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          207  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     208  "         4-Formyl-N,N-diethylaniline                                     209  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         210  "         4-Formyl-N,N-diethyl-m-toluidine                                211  "         4-Formyl-N,N-diethyl-m-chloroaniline                            212  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     213  "         4-Formyl-N,N-diethyl-o-bromoaniline                             214  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    215  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         216  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             217  "         4-Formyl-N,N-dibenzyl aniline                                   218  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-                                    succinimidoethyl)-m-toluidine                                   219  "         4-Formyl-N-phenylthiomorpholinedioxide                          220  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-                                 m-toluidine                                                     221  2-thienyl 6-Formyl-N-ethyl-1,2,3,                                                        4-tetrahydro-2,2,4,                                                            7-tetramethylquinoline                                          222  "         6-Formyl-N-(β-mercaptobenzthiazolylethyl)                                 1,2,3,4-tetrahydro-2,2,4-trimethylquinoline                     223  "         4-Formyl-N,N-diethylaniline                                     224  "         4-Formyl-N-ethyl-                                                              N-(β-phthalimidoethyl)-m-toluidine                         225  "         4-Formyl-N,N-diethyl-m-toluidine                                226  "         4-Formyl-N,N-diethyl-m-chloroaniline                            227  "         4-Formyl-N-ethyl-N-(β-chloroethyl)                                        m-toluidine                                                     228  "         4-Formyl-N,N-diethyl-o-bromoaniline                             229  "         4-Formyl-N-ethyl-                                                              N-(β-cyanoethyl)aniline                                    230  "         4-Formyl-N-ethyl-                                                              N-(β-succinimidoethyl)-m-toluidine                         231  "         4-Formyl-N-(β-cyanoethyl)-                                                N-(β-succinimidoethyl)-aniline                             232  "         4-Formyl-N,N-dibenzyl ailine                                    233  "         4-Formyl-N-(β-acetoxyethyl)-N-(β-                                    succinimidoethyl)-m-toluidine                                   234  "         4-Formyl-N-phenylthiomorpholinedioxide                          235  "         4-Formyl-N-(cyclohexyl)-N-(β-cyanoethyl)-                                 m-toluidine                                                     __________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

I claim:
 1. A compound of the formula ##STR44## in which R₁ and R₂ are the same or different and selected from hydrogen, aryl, benzyl, cyclohexyl, C₁ -C₆ alkyl, C₁ -C₆ alkyl substituted with Cl, CN, OC₂ H₄ OC₂ H₅, C₁ -C₄ alkoxy, aryl, ##STR45## in which the aryl, and the C₁ -C₁₀ alkyl of the preceding substituent are unsubstituted or substituted with Cl, Br, CN, NO₂, CO--alkyl, CO--aryl, alkoxy, aryloxy, CO--O--alkyl or CO--O--aryl, ##STR46## NHCONHPh, OCONHPh, phthalimido, succinimido and mercaptobenzothiazolyl; ##STR47## is selected from piperidino, morpholino, thiomorpholino, and piperazino; R₃ is H, Cl, Br, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; ring A is unsubstituted or substituted with 1-3 methyl groups; R₄ is H, Cl, Br, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; and R₅ is selected from 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl, and these heterocycles substituted with Cl, Br, NO₂, CN, aryl, aryl substituted with Cl, Br, NO₂, or CN, C₁ -C₄ alkyl, or COOR₆ wherein R₆ is C₁ -C₄ alkyl or aryl.
 2. A compound according to claim 1 having the formula ##STR48##
 3. A compound according to claim 1 having the formula ##STR49##
 4. A compound according to claim 1 having the formula ##STR50##
 5. A compound according to claim 1 having the formula ##STR51##
 6. A compound according to claim 1 having the formula ##STR52## 